Polyurethane elastomer for corrosion prevention of submarine pipeline joint and preparation method thereof

文档序号：644750 发布日期：2021-05-14 浏览：12次中文

阅读说明：本技术 海底管道节点防腐用聚氨酯弹性体及其制备方法 (Polyurethane elastomer for corrosion prevention of submarine pipeline joint and preparation method thereof ) 是由陈海良韩胜奎盖志科房玉俊于 2020-12-30 设计创作，主要内容包括：本发明涉及一种海底管道节点防腐用聚氨酯弹性体及其制备方法,属于聚氨酯弹性体技术领域。本发明所述的海底管道节点防腐用聚氨酯弹性体,A组分：包括扩链交联剂、催化剂、增塑剂、抗氧剂、聚醚多元醇、助剂；所述聚醚多元醇为二官能度的聚四氢呋喃多元醇、二官能度的聚醚多元醇或三官能度的聚醚多元醇中的一种或多种；B组分：为以二异氰酸酯和聚醚多元醇为原料,反应得到的异氰酸根质量含量为20.0％～25.0％的预聚物。本发明所述的海底管道节点防腐用聚氨酯弹性体,不仅具有良好的耐腐蚀性能,在深水中高低温硬度变换不大,还具有良好的力学性能；本发明同时提供了简单易行的制备方法。(The invention relates to a polyurethane elastomer for corrosion prevention of submarine pipeline joints and a preparation method thereof, and belongs to the technical field of polyurethane elastomers. The invention relates to a polyurethane elastomer for corrosion prevention of submarine pipeline joints, which comprises the following components in part by weight: comprises a chain extension crosslinking agent, a catalyst, a plasticizer, an antioxidant, polyether polyol and an auxiliary agent; the polyether polyol is one or more of difunctional polytetrahydrofuran polyol, difunctional polyether polyol or trifunctional polyether polyol; and B component: the prepolymer is prepared by reacting diisocyanate and polyether polyol as raw materials to obtain a prepolymer with the mass content of isocyanic acid radical of 20.0-25.0%. The polyurethane elastomer for preventing corrosion of the submarine pipeline joint has good corrosion resistance, small hardness change at high and low temperatures in deep water and good mechanical property; the invention also provides a simple and feasible preparation method.)

1. The utility model provides a submarine pipeline node is anticorrosive uses polyurethane elastomer which characterized in that: comprises a component A and a component B, wherein,

the component A comprises: comprises a chain extension crosslinking agent, a catalyst, a plasticizer, an antioxidant, polyether polyol and an auxiliary agent;

the polyether polyol is one or more of difunctional polytetrahydrofuran polyol, difunctional polyether polyol or trifunctional polyether polyol;

the number average molecular weight of the difunctional polytetrahydrofuran polyalcohol is 650-2000;

the number average molecular weight of the bifunctional polyether polyol is 400-4000;

the number average molecular weight of the trifunctional polyether polyol is 375-6000;

and B component: the prepolymer is prepared by reacting diisocyanate and polyether polyol as raw materials to obtain a prepolymer with the mass content of isocyanic acid radical of 20.0-25.0%.

2. The polyurethane elastomer for corrosion protection of submarine pipeline joints according to claim 1, wherein: the component A comprises the following raw materials in percentage by mass: 14.6 to 21.4 percent of chain-extending cross-linking agent, 14.6 to 53.6 percent of polyether diol, 14.6 to 58.5 percent of polyether triol, 1.0 to 3.0 percent of 3A molecular sieve, 0 to 9.7 percent of plasticizer, 0.1 to 0.3 percent of antioxidant and 0.1 to 0.3 percent of catalyst.

3. The polyurethane elastomer for corrosion protection of submarine pipeline joints according to claim 2, wherein: the polyether diol is PPG1000 or PPG2000, and the polyether triol is one or two of PPG125 or EP-330 NG.

4. The polyurethane elastomer for corrosion protection of submarine pipeline joints according to claim 1, wherein: the antioxidant is one or more of 1010, 1076 or 1035.

5. The polyurethane elastomer for corrosion protection of submarine pipeline joints according to claim 1, wherein: the catalyst is one or more of bismuth catalyst, zinc catalyst, amine catalyst, tin catalyst or mercury catalyst.

6. The polyurethane elastomer for corrosion protection of submarine pipeline joints according to claim 1, wherein: the chain extension cross-linking agent is one or more of an amine chain extender or an alcohol chain extender.

7. The polyurethane elastomer for corrosion protection of submarine pipeline joints according to claim 1, wherein: the plasticizer is one or more of dioctyl terephthalate, dioctyl phthalate, dimethyl ethylene glycol phthalate or diisobutyl phthalate.

8. The polyurethane elastomer for corrosion protection of submarine pipeline joints according to claim 1, wherein: the component B comprises the following raw materials in percentage by mass:

68.8 to 81 percent of diisocyanate,

19.0 to 31.2 percent of polyether polyol.

9. The polyurethane elastomer for corrosion protection of submarine pipeline joints according to claim 1, wherein: the diisocyanate is one or more of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2, 4' -diphenylmethane diisocyanate, 4' -diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, 4' -dicyclohexylmethane diisocyanate or isophorone diisocyanate.

10. A method for preparing the polyurethane elastomer for corrosion protection of the submarine pipeline joint according to any one of claims 1 to 9, which is characterized in that: the method comprises the following steps:

(1) mixing polyether polyol and a plasticizer in the component A, heating to 100-120 ℃, dehydrating until the water content is less than 0.05%, cooling to 80-90 ℃, adding a chain extension crosslinking agent, stirring for 25-35min, cooling to 70-75 ℃, and adding an antioxidant, a catalyst and an auxiliary agent to obtain the component A;

(2) mixing all the raw materials of the component B, reacting for 2-3 hours at 80-85 ℃, and removing bubbles in vacuum to obtain a prepolymer with the mass content of isocyanic acid radical of 20.0-25.0%;

(3) cooling the component A and the component B to normal temperature, and then mixing the components in a mass ratio of 100: 80-100, pouring a test piece on a normal-temperature grinding tool, drying the surface of the test piece to obtain a sample, and standing and cooling the sample at normal temperature to obtain the polyurethane elastomer for preventing the corrosion of the submarine pipeline node.

Technical Field

The invention relates to a polyurethane elastomer for corrosion prevention of submarine pipeline joints and a preparation method thereof, and belongs to the technical field of polyurethane elastomers.

Background

In recent years, with the depletion of continental oil fields, mankind has gradually turned his eyes to marine oil fields, where abundant energy sources are stored, and petroleum and natural gas are among them. The seabed oil and gas pipeline is an important facility for transporting oil and gas energy and is an important component in a marine oil field production system. The offshore oil field is further connected with a continental petroleum industrial system through connecting the oil gas gathering, transportation, storage and transportation systems of the offshore oil field by a submarine oil gas pipeline. With the continuous development of offshore oil fields in China, the demand for submarine oil and gas pipeline facilities is greatly increased. However, how the connection point between the pipes (pipe joint) is sealed and corrosion-resistant is a difficult problem.

At present, on one hand, a heat insulation layer of a submarine pipeline for heat insulation conveying is made of polyurethane foam, the heat insulation effect is good, the closed pore rate is not 100%, the compressive strength is limited, and once the submarine pipeline is damaged, water can invade the whole heat insulation layer, so that heat insulation failure is caused. On the other hand, with exploitation of oil fields from shallow water to deep water, the requirements on submarine pipelines are higher and higher, influence of factors in the aspects of seawater erosion, sea waves, gravels, high pressure and the like is comprehensively considered, and the requirements on the performance of an anticorrosive coating of a submarine oil and gas pipeline node are extremely important.

Disclosure of Invention

The invention aims to solve the technical problem of overcoming the defects in the prior art, and provides a polyurethane elastomer for corrosion prevention of a submarine pipeline joint, which has good corrosion resistance, small change of high and low temperature hardness in deep water and good mechanical property; the invention also provides a simple and feasible preparation method.

The polyurethane elastomer for preventing corrosion of the submarine pipeline joint comprises a component A and a component B, wherein,

the component A comprises: comprises a chain extension crosslinking agent, a catalyst, a plasticizer, an antioxidant, polyether polyol and an auxiliary agent;

the polyether polyol is one or more of difunctional polytetrahydrofuran polyol, difunctional polyether polyol or trifunctional polyether polyol;

the number average molecular weight of the difunctional polytetrahydrofuran polyalcohol is 650-2000;

the number average molecular weight of the bifunctional polyether polyol is 400-4000;

the number average molecular weight of the trifunctional polyether polyol is 375-6000;

and B component: the prepolymer is prepared by reacting diisocyanate and polyether polyol as raw materials to obtain a prepolymer with the mass content of isocyanic acid radical of 20.0-25.0%.

Preferably, the component A comprises the following raw materials in percentage by mass: 14.6 to 21.4 percent of chain-extending cross-linking agent, 14.6 to 53.6 percent of polyether diol, 14.6 to 58.5 percent of polyether triol, 1.0 to 3.0 percent of 3A molecular sieve, 0 to 9.7 percent of plasticizer, 0.1 to 0.3 percent of antioxidant and 0.1 to 0.3 percent of catalyst.

Preferably, the polyether diol is PPG1000 or PPG2000, and the polyether triol is one or both of PPG125 or EP-330 NG.

Preferably, the antioxidant is one or more of 1010, 1076, or 1035.

Preferably, the catalyst is one or more of a bismuth-based catalyst, a zinc-based catalyst, an amine-based catalyst, a tin-based catalyst, or a mercury-based catalyst.

Preferably, the chain-extending cross-linking agent is a mixture of an amine chain-extending agent and an alcohol chain-extending agent. The amine chain extender is preferably MOCA; the alcohol chain extender is preferably one or more of ethylene glycol, propylene glycol, diethylene glycol, 1, 4-butanediol or 1, 6-hexanediol.

Preferably, the plasticizer is a benzoate plasticizer, and more preferably one or more of dioctyl terephthalate, dioctyl phthalate, dimethyl ethylene glycol phthalate, or diisobutyl phthalate.

Preferably, the component B comprises the following raw materials in percentage by mass:

68.8 to 81 percent of diisocyanate,

19.0 to 31.2 percent of polyether polyol.

Preferably, the diisocyanate is one or more of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2, 4' -diphenylmethane diisocyanate, 4' -diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, 4' -dicyclohexylmethane diisocyanate, or isophorone diisocyanate.

The preparation method of the polyurethane elastomer for corrosion prevention of the submarine pipeline node comprises the following steps:

The chain extension cross-linking agent used in the invention is a mixture of amines and alcohols, wherein the amine chain extension agent is used for improving the gel speed and generating a large amount of heat, providing energy for the alcohol chain extension agent in the reaction and accelerating the strength.

Compared with the prior art, the invention has the following beneficial effects:

(1) the prepared polyurethane elastomer for corrosion prevention of the submarine pipeline joint has good fluidity, is easy to operate and environment-friendly, has high strength and high hardness to meet construction requirements and save time and cost, the hardness can reach Shore hardness 45D after 3-5min, the polyurethane elastomer can be directly dragged into the ocean for installation and construction, post-vulcanization is not needed for products, and the final hardness can reach 60D;

(2) the prepared polyurethane elastomer for corrosion prevention of the submarine pipeline joint has a regular structure and good micro-phase separation, still has good mechanical properties on the seabed, can resist the corrosion of seawater and sand and has a certain heat preservation effect;

(3) when the polyurethane elastomer for corrosion prevention of the submarine pipeline joint is prepared, the polyurethane elastomer is poured at normal temperature, and has sufficient operability, so that the polyurethane elastomer is suitable for smooth and rough surfaces;

(4) the preparation method provided by the invention has simple and reasonable process and is easy for industrial production.

Detailed Description

The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.

The parameters of the raw materials used are as follows:

PTMG 2000: number average molecular weight 2000, functionality of 2, polyether polyol, basf (china) ltd;

DL 1000: number average molecular weight 1000, functionality 2, polyether polyol, Shandong New materials, Inc.;

DL 400: number average molecular weight 400, functionality 2, polyether polyol, Shandong Lanxingdong GmbH;

DL 3000: number average molecular weight 3000, functionality 2, polyether polyol, Shandong New materials, Inc.;

EP-330 NG: number average molecular weight 4800, functionality 3, polyether polyol, Shandong Lanxingdao Co., Ltd;

DV 125: number average molecular weight 375, functionality 3, polyether polyol, Shandong Lanxingdao Co., Ltd;

MDI-50, number average molecular weight 250, diphenylmethane diisocyanate, Tantawawa chemical group, Inc.;

MDI-100, number average molecular weight 250, diphenylmethane diisocyanate, Tantawawa chemical group, Inc.;

CD-C, number average molecular weight 300, modified diphenylmethane diisocyanate, Corsik Polymer, China Co., Ltd;

MOCA number average molecular weight 267, 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, Suzhou Xiangyuan New materials GmbH;

KC-22: number average molecular weight 106, diethylene glycol, Shandong Feier New materials, Inc.;

CB-18: bismuth neodecanoate, taixing, inc, Jiangsu province;

a3: n, N-dimethylcyclohexane, alfa aesar (china) chemical ltd;

1076: antioxidants, n-octadecyl propionate, Hengqiao industries, Inc. (Taibei/Dongguan/Nanjing);

1010: antioxidants, pentaerythritol esters, hoechwan ltd, beijing;

1035 of isooctyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, Hubei Qifei pharmaceutical chemical Co., Ltd;

3A molecular sieve: water absorbent, aust catalyst materials (Dalian) Limited;

Z-A is diluent, Istman.

Example 1

The preparation steps of the prepolymer B component are as follows:

based on 100 parts by weight of the total weight of the component B, 20.6 parts by weight of polyether polyol (DL-3000) with the molecular weight of 3000, 8.9 parts by weight of polyether polyol (DL-400) with the molecular weight of 400, 14.1 parts by weight of CD-C, 42.3 parts by weight of MDI-100 and 14.1 parts by weight of MDI-50 are reacted for 2 hours at 85 ℃, and bubbles are removed under the vacuum (-0.095MPa) condition to obtain a prepolymer with the content of isocyanate groups of 20.5 percent.